Solid pigment preparations comprising surface-active additives based on alkoxylated bisphenols

ABSTRACT

The invention related to solid pigment preparations essentially comprising the following components: (A) 60 to 90 wt. % of at least one pigment and (B) 10 to 40 wt. % of at last one surface active additive from the group of reaction products of alkylene oxides with a bisphenol of the general formula (I) in which the rings A are each mono- or di-substituted by C 1 -C 8  alkyl, phenyl or phenyl C 1 -C 9  alkyl and R 1  and R 2  independently=H, or C 1 -C 8  alkyl, methods for production thereof and for dyeing high molecular weight organic and inorganic materials.

The present invention relates to solid pigment preparations comprisingas essential constituents

-   -   (A) from 60 to 90% by weight of at least one pigment and    -   (B) from 10 to 40% by weight of at least one surface-active        additive from the group of the reaction products of alkylene        oxides with a bisphenol of the general formula I    -   where the rings A may each be substituted by one or two        substituents selected from the group consisting of C₁-C₈-alkyl,        phenyl and phenyl-C₁-C₈-alkyl and R¹ and R² are independently        hydrogen or C₁-C₈-alkyl.

The present invention further relates to the production of these pigmentpreparations and to their use for pigmenting macromolecular organic andinorganic materials.

Liquid systems such as coatings, varnishes, emulsion paints and printinginks are customarily colored using pigment formulations which includewater, organic solvent or mixtures thereof. As well as anionic,cationic, nonionic or amphoteric dispersants, these pigment formulationsgenerally have to be additized with further assistants, such asdried-crust inhibitors, freeze resistance enhancers, thickeners andanti-skinners, for stabilization.

There is a need for novel pigment preparations which are comparable tothe liquid formulations with regard to color properties anddispersibility, but do not require the additions mentioned and areeasier to handle. However, simply drying the liquid formulations doesnot provide solid pigment preparations having comparable performanceproperties.

DE-A-199 05 269 describes solid pigment formulations which includedispersants based on nonionic or ionic modified phenol-styrenepolyglycol ethers or mixtures of ethoxylated castor oil with minoramounts of these ethers or of phosphonic esters and additionally alwaysa thickener based on optionally partially hydrogenated polyvinyl alcoholor on anionic polyhydroxy compounds and are used for pigmentingwaterborne application media.

EP-A-84 645 and 403 917 disclose highly concentrated, solid pigmentformulations for coloring aqueous, alcoholic and aqueous-alcoholiccoatings and printing inks that include up to 30% by weight of anadditive based on reaction products of at least bifunctional amines withpropylene oxide and ethylene oxide.

U.S. Pat. Nos. 4,056,402 and 4,127,422 describe dry nondusting pigmentcompositions for waterborne finish systems. However, these pigmentcompositions, as well as nonionic dispersants, include as an essentialconstituent at least 10% by weight of water-soluble cellulose ethers orof water-dispersible polyvinyl compounds and hence differ from thepigment preparations of the present invention.

EP-A-1 081 195 discloses granular pigment preparations for pigmentingplastics. These pigment preparations include nonionic polyethylene waxadditives and are produced by contacting the pigments with the waxes inthe course of solvent finishing and spray drying. However, thisproduction process is only useful for organic pigments which arefinished in organic solvents.

Finally, the documents DE-A-102 04 304 and also 102 04 583, 102 27 657and 102 28 199, each unpublished at the priority date of the presentinvention, describe the use of solid pigment preparations which includenonionic surface-active additives based on polyethers or mixtures ofthese additives with anionic surface-active additives based onappropriately modified polyethers.

It is an object of the present invention to provide solid pigmentpreparations having altogether advantageous application properties,especially high color strength and particularly good stir-indispersibility in a wide variety of application media and also highstability in storage.

We have found that this object is achieved by the pigment preparationsdefined at the beginning.

The present invention further provides a process for producing pigmentpreparations which comprises wet-comminuting the pigment (A) in aqueoussuspension in the presence of some or all of additive (B) and thendrying the suspension, if necessary after the rest of additive (B) hasbeen added.

The present invention yet further provides a process for pigmentingmacromolecular organic or inorganic materials, which comprisesintroducing the pigment preparations into these materials by stirring orshaking.

The pigment preparations of the present invention include as essentialconstituents a pigment (A) and a surface-active additive (B).

Component (A) in the pigment preparations of the present invention maybe an organic pigment or an inorganic pigment. It will be appreciatedthat the pigment preparations may also include mixtures of variousorganic or various inorganic pigments or mixtures of organic andinorganic pigments.

The pigments are present in finely divided form. Accordingly thepigments typically have average particle sizes from 0.1 to 5 μm,especially from 0.1 to 3 μm and in particular from 0.1 to 1 μm.

The organic pigments are typically organic chromatic and black pigments.Inorganic pigments can likewise be color pigments (chromatic, black andwhite pigments) and also luster pigments and the inorganic pigmentstypically used as fillers.

There now follow examples of suitable organic color pigments:

-   -   monoazo pigments:        -   C.I. Pigment Brown 25;        -   C.I. Pigment Orange 5, 13, 36, 38, 64 and 67;        -   C.I. Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31,            48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:1, 52:2, 53,            53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175,            184, 185, 187, 191:1, 208, 210, 245, 247 and 251;        -   C.I. Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154,            168, 181, 183 and 191;        -   C.I. Pigment Violet 32;    -   disazo pigments: C.I. Pigment Orange 16, 34, 44 and 72;        -   C.I. Pigment Red 144, 166, 214, 220, 221 and 242;        -   C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113,            126, 127, 155, 174, 176, 180 and 188;    -   disazo condensation pigments:        -   C.I. Pigment Yellow 93, 95 and 128;        -   C.I. Pigment Red 144, 166, 214, 220, 242 and 262;        -   C.I. Pigment Brown 23 and 41;    -   anthanthrone pigments:        -   C.I. Pigment Red 168;    -   anthraquinone pigments:        -   C.I. Pigment Yellow 147, 177 and 199;        -   C.I. Pigment Violet 31;    -   anthrapyrimidine pigments:        -   C.I. Pigment Yellow 108;    -   quinacridone pigments:        -   C.I. Pigment Orange 48 and 49;        -   C.I. Pigment Red 122, 202, 206 and 209;        -   C.I. Pigment Violet 19;    -   quinophthalone pigments:        -   C.I. Pigment Yellow 138;    -   diketopyrrolopyrrole pigments:        -   C.I. Pigment Orange 71, 73 and 81;        -   C.I. Pigment Red 254, 255, 264, 270 and 272;    -   dioxazine pigments:        -   C.I. Pigment Violet 23 and 37;        -   C.I. Pigment Blue 80;    -   flavanthrone pigments:        -   C.I. Pigment Yellow 24;    -   indanthrone pigments:        -   C.I. Pigment Blue 60 and 64;    -   isoindoline pigments:        -   C.I. Pigment Orange 61 and 69;        -   C.I. Pigment Red 260;        -   C.I. Pigment Yellow 139 and 185;    -   isoindolinone pigments:        -   C.I. Pigment Yellow 109, 110 and 173;    -   isoviolanthrone pigments:        -   C.I. Pigment Violet 31.;    -   metal complex pigments:        -   C.I. Pigment Red 257;        -   C.I. Pigment Yellow 117, 129, 150, 153 and 177;        -   C.I. Pigment Green 8;    -   perinone pigments:        -   C.I. Pigment Orange 43;        -   C.I. Pigment Red 194;    -   perylene pigments:        -   C.I. Pigment Black 31 and 32;        -   C.I. Pigment Red 123, 149, 178, 179, 190 and 224;        -   C.I. Pigment Violet 29;    -   phthalocyanine pigments:        -   C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16;        -   C.I. Pigment Green 7 and 36;    -   pyranthrone pigments:        -   C.I. Pigment Orange 51;        -   C.I. Pigment Red 216;    -   pyrazoloquinazolone pigments:        -   C.I. Pigment Orange 67;        -   C.I. Pigment Red 251;    -   thioindigo pigments: p2 Pigment Red 88 and 181;        -   C.I. Pigment Violet 38;    -   triarylcarbonium pigments:        -   C.I. Pigment Blue 1, 61 and 62;        -   C.I. Pigment Green 1;        -   C.I. Pigment Red 81, 81:1 and 169;        -   C.I. Pigment Violet 1, 2, 3 and 27;    -   C.I. Pigment Black 1 (aniline black);    -   C.I. Pigment Yellow 101 (aldazine yellow);    -   C.I. Pigment Brown 22.

Examples of suitable inorganic color pigments are:

-   -   white pigments: titanium dioxide (C.I. Pigment White 6), zinc        white, pigment grade zinc oxide;        -   zinc sulfide, lithopone;    -   black pigments:        -   iron oxide black (C.I. Pigment Black 11),        -   iron manganese black, spinel black (C.I. Pigment Black 27);            carbon black (C.I. Pigment Black 7);    -   chromatic pigments:        -   chromium oxide, chromium oxide hydrate green; chrome green            (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green            50); ultramarine green;        -   cobalt blue (C.I. Pigment Blue 28 and 36; C.I. Pigment Blue            72); ultramarine blue; manganese blue;        -   ultramarine violet; cobalt violet and manganese violet;        -   red iron oxide (C.I. Pigment Red 101); cadmium sulfoselenide            (C.I. Pigment Red 108); cerium sulfide (C.I. Pigment Red            265); molybdate red (C.I. Pigment Red 104); ultramarine red;        -   brown iron oxide (C.I. Pigment Brown 6 and 7), mixed brown,            spinel phases and corundum phases (C.I. Pigment Brown 29,            31, 33, 34, 35, 37, 39 and 40), chromium titanium yellow            (C.I. Pigment Brown 24), chrome orange;        -   cerium sulfide (C.I. Pigment Orange 75); yellow iron oxide            (C.I. Pigment Yellow 42); nickel titanium yellow (C.I.            Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160,            161, 162, 163, 164 and 189); chromium titanium yellow;            spinel phases (C.I. Pigment Yellow 119); cadmium sulfide and            cadmium zinc sulfide (C.I. Pigment Yellow 37 and 35); chrome            yellow (C.I. Pigment Yellow 34); bismuth vanadate (C.I.            Pigment Yellow 184).

Examples of inorganic pigments typically used as fillers are transparentsilicon dioxide, ground quartz, aluminum oxide, aluminum hydroxide,natural micas, natural and precipitated chalk and barium sulfate.

Luster pigments are platelet-shaped pigments having a monophasic orpolyphasic construction whose color play is marked by the interplay ofinterference, reflection and absorption phenomena. Examples are aluminumplatelets and aluminum, iron oxide and mica platelets bearing one ormore coats, especially of metal oxides.

Component (B) of the pigment preparations according to the presentinvention is at least one surface-active additive from the group of thereaction products of alkylene oxides with a bisphenol of the formula I.

Said bisphenol I is preferably an unsubstituted bisphenol A(R¹═R²═—CH₃). Substituted bisphenol A is particularly suitable as well,especially bisphenol A which has been reacted with styrene and issubstituted by a total of 4 phenyl-1-ethyl radicals ortho to the two OHgroups.

The alkylene oxides are preferably C₂-C₄-alkylene oxides, and morepreferably ethylene oxide and propylene oxide.

Said bisphenol I can have been reacted with just one alkylene oxide orelse with various alkylene oxides. When the reaction products arepolymers, random polymers or preferably block copolymers can be formedwhen various alkylene oxides are used. Preferably, the bisphenol I isreacted first with propylene oxide and then with ethylene oxide, but thereactions may also be carried out in another order.

In general, the additives (B) contain from 4 to 150 mol of alkyleneoxide per mole of bisphenol I.

Useful surface-active additives (B) are not only the nonionic alkyleneoxide adducts themselves but also their acid sulfuric or sulfonic esters(obtained by reaction with sulfuric acid or sulfonic acid) andespecially water-soluble salts thereof, especially alkali metal salts,in particular sodium salts, and ammonium salts. Such anionic additives(B) are based in particular on the above-describedphenylethyl-substituted bisphenol A derivative.

The pigment preparations of the present invention preferably include theadditives (B) in nonionic form.

Particularly preferred additives (B) are the reaction products ofbisphenol A with propylene oxide and preferably with ethylehe oxide thatcontain from 4 to 150 mol, especially from 4 to 100 mol and inparticular from 4 to 50 mol of the alkylene oxide per mole of bisphenolA.

Such surface-active additives are known and are commercially availablefor example under the names of Pluriol® (BASF) and Atlas® (Uniqema).

The pigment preparations of the present invention include from 60 to 90%by weight and preferably from 70 to 85% by weight of component (A) andfrom 10 to 40% by weight, and preferably from 15 to 30% by weight ofcomponent (B).

The pigment preparations according to the present invention areadvantageously obtainable by the production process of the invention bywet-comminuting the pigment (A) in aqueous suspension in the presence ofsome or all of additive (B) and then drying the suspension, if necessaryafter the rest of additive (B) has been added.

Pigment (A) can be used in the process of the present invention as a drypowder or in the form of a presscake.

The pigment (A) as used is preferably a finished product, ie the primaryparticle size of the pigment has already been adjusted to the desiredapplication value. This finish is advisable in the case of organicpigments especially, since the as-synthesized crude material isgenerally not directly suitable for use. In the case of inorganicpigments, for example in the case of oxide and bismuth vanadatepigments, the primary particle size can also be adjusted in the courseof the synthesis of the pigment, so that the as-synthesized pigmentsuspensions can be used directly in the process of the presentinvention.

Since the finished pigment (A) typically reagglomerates in the course ofdrying or on the filter assembly, it is subjected to wet comminution,for example grinding in a stirred media mill, in aqueous suspension.

The wet comminution should be carried out in the presence of at least aportion of the additive (B) for the ready-produced pigment preparation,and it is preferable to add the entire amount of additive (B) prior tothe wet comminution.

The particle size of the pigment preparations of the present inventioncan be controlled to a specific value, depending on the chosen method ofdrying—spray granulation and fluidized bed drying, spray drying, dryingin a paddle dryer, evaporation and subsequent comminution.

Spray and fluidized bed granulation may produce coarsely dividedgranules having average particle sizes from 50 to 5 000 μm, andespecially from 100 to 1 000 μm. Spray drying typically producesgranules having average particle sizes <20 μm. Finely dividedpreparations are obtainable by drying in a paddle dryer and byevaporation with subsequent grinding. Preferably, however, the pigmentpreparations of the present invention are in granule form.

Spray granulation is preferably carried out in a spray tower using aone-material nozzle. Here, the suspension is sprayed in the form ofrelatively large drops, and the water evaporates. The additive (B) meltsat the drying temperatures and so leads to the formation of asubstantially spherical granule having a particularly smooth surface(BET values generally ≦15 m²/g, and especially ≦10 m²/g).

The gas inlet temperature in the spray tower is generally in the rangefrom 180 to 300° C. and preferably in the range from 150 to 300° C. Thegas outlet temperature is generally in the range from 70 to 150° C. andpreferably in the range from 70 to 130° C.

The residual moisture content of the granular pigment obtained ispreferably <2% by weight.

The pigment preparations of the present invention are notable in use fortheir excellent color properties which are comparable to those of liquidpigment formulations, especially with regard to color strength,brilliance, hue and hiding power, and in particular for their stir-incharacteristics, ie they can be dispersed in application media with aminimal input of energy, simply by stirring or shaking. This applies inparticular to the coarsely divided pigment granules, which constitutethe preferred embodiment of the pigment preparations of the presentinvention. Compared with liquid pigment formulations, the pigmentpreparations of the present invention additionally have the followingadvantages: They have a higher pigment content. Whereas liquidformulations tend to change viscosity during storage and have to beadmixed with preservatives and agents for enhancing the resistance tofreezing and/or drying out (crusting), the pigment preparations of thepresent invention exhibit very good stability in storage. They are botheconomically and ecologically advantageous with regard to packaging,storage and transportation. Since they are solvent free, they are moreflexible in use.

The pigment preparations of the present invention which are in granuleform are notable for excellent attrition resistance, a minimal tendencyto compact or clump, uniform particle size distribution, goodpourability, flowability and meterability and also dustlessness inhandling and application.

The pigment preparations of the present invention are very useful forpigmenting macromolecular organic and inorganic materials of any kind.Liquid application media in this context can be purely aqueous; comprisemixtures of water and organic solvents, for example alcohols; or bebased exclusively on organic solvents, such as alcohols, glycol ethers,ketones, eg methyl ethyl ketone, amides, eg N-methylpyrrolidone anddimethylformamide, esters, eg ethyl acetate, butyl acetate andmethoxypropyl acetate, or aromatic or aliphatic hydrocarbons, eg xylene,mineral oil and mineral spirits.

If desired, the preparations can initially be stirred into a solventwhich is compatible with the particular application medium, again withminimal input of energy, and then be introduced into this applicationmedium. For instance, slurries of pigment preparations in glycols orother solvents customary in the paint and coatings industry, such asmethoxypropyl acetate, can be used to render the pigment preparationsfor aqueous systems compatible with hydrocarbonaceous systems or systemsbased on nitrocellulose.

Examples of materials which can be pigmented with the pigmentpreparations of the present invention include: coatings, for examplearchitectural coatings, industrial coatings, automotive coatings,radiation-curable coatings; paints, including paints for buildingexteriors and building interiors, for example wood paints, lime washes,distempers, emulsion paints; solventborne printing inks, for exampleoffset printing inks, flexographic printing inks, toluene gravureprinting inks, textile printing inks, radiation-curable printing inks;waterborne inks, including inkjet inks; color filters; buildingmaterials (water is typically added only after building material andgranular pigment have been dry mixed), for example silicate rendersystems, cement, concrete, mortar, gypsum; bitumen, caulks; cellulosicmaterials, for example paper, paperboard, cardboard, wood and woodbase,which can each be coated or otherwise finished; adhesives; film-formingpolymeric protective colloids as used for example in the pharmaceuticalindustry; cosmetic articles; detergents.

The pigment preparations of the present invention are particularlyuseful as mixing components in color-mixing or -matching systems. Owingto their stir-in characteristics, they can be used directly as a solidfor this purpose. If desired, however, they can also be first convertedinto base colors, mixing varnishes and tinting colors (especially intocolors having a high solids content, “HS colors”), or even more highlypigmented tinting pastes which then constitute the components of themixing system. The matching of the desired hue and hence the mixing ofthe color components can be effected visually via a system of colorcards in a very large number of hue gradations which are based on colorstandards, such as RAL, BS and NCS, or preferably under computercontrol, whereby an unlimited number of hues become accessible(“computer color matching”).

The pigment preparations of the present invention are also very usefulfor pigmenting plastics and powder coatings. They may be incorporatedinto the plastics and powder coatings by extruding, rolling, kneading orgrinding.

EXAMPLES

Making and testing of granular pigment preparations according to thepresent invention

The pigment granules were made by a suspension of x kg of finishedpigment (A) and y kg of additive (B) in 150 kg of water being ballmilled to a d₅₀ value of <1 μm and then spray granulated in a spraytower using a one-material nozzle at a gas inlet temperature of 165° C.and a gas outlet temperature of 70° C.

The additives used were as follows:

-   -   B1: ethoxylated bisphenol A (15 mol of EO/mol of bisphenol A).    -   B2: Monosulfated ethoxylated tetraphenylethyl-substituted        bisphenol A (100 mol of EO/mol of bisphenol A; U.S. Pat. No. 4        218 218: surfactant 13).

The color strength of the pigment granules was determinedcolorimetrically in the white reduction (reported in terms of the DIN55986 coloring equivalents CEs) in a waterborne emulsion paint. To thisend, a mixture of in each case 1.25 g of granular pigment and 50 g of awaterborne styrene-acrylate-based test binder having a white pigmentcontent of 16.4% by weight (TiO₂, Kronos 2043) (BASF test binder00-1067) were homogenized in a 150 ml plastic beaker by running a highspeed stirrer at 1 500 rpm for 3 min. The color obtained was then drawndown on a black and white test card using a 100 μn wire-wound filmapplicator and dried for 30 min.

The respectively corresponding emulsion paints made using commerciallyavailable aqueous formulations of the pigments were each assigned the CEvalue of 100 (standard). CE values <100 mean a higher color strengththan that of the standard, CE>100 accordingly a lower color strength.

In addition, the color strength was assessed after five days of storageat 40° C.

The table hereinbelow lists the compositions of the pigment granulesproduced and the CE values obtained in each case. TABLE Pigment AdditiveCE Ex (A) x kg (B) y kg instantly 5 d/40° C. 1 P.V. 23 78 B1 22 100 1002 P.V. 23 78 B2 22 100 100 3 P.R. 122 75 B1 25  98  99 4 P.R. 122 75 B225 100 100 5 P.Y. 74 77 B1 23 100 100 6 P.Y. 74 77 B2 23 105 105

1. A solid pigment preparation comprising (A) from 60 to 90% by weight of at least one pigment and (B) from 10 to 40% by weight of at least one surface-active additive from the group of the reaction products of alkylene oxides with a bisphenol of the general formula I

where the rings A may each be substituted by one or two substituents selected from the group consisting of C₁-C₈-alkyl, phenyl and phenyl-C₁-C₈-alkyl and R¹ and R² are each methyl.
 2. A solid pigment preparation as claimed in claim 1, wherein component (B) is at least one additive selected from the group consisting of the reaction products of ethylene oxide and/or propylene oxide with bisphenol A and phenylethyl-substituted bisphenol A, the acidic sulfuric and sulfonic esters of these alkylene oxide compounds and the salts of these esters.
 3. A solid pigment preparation as claimed in claim 1, wherein component (B) is at least one nonionic surface-active additive based on reaction products of bisphenol A with from 4 to 150 mol of ethylene oxide/mol.
 4. A solid pigment preparation as claimed in claim 1, in the form of granules having an average particle size from 50 to 5000 μm and a BET surface area≦15 m²/g.
 5. A process for producing a solid pigment preparation as claimed in claim 1, comprising wet-comminuting the pigment (A) in aqueous suspension in the presence of some or all of additive (B) and then drying the suspension, if necessary after the rest of additive (B) has been added.
 6. A process for pigmenting macromolecular organic and inorganic materials, comprising introducing the solid pigment preparation as claimed in claim 1 into said macromolecular organic and inorganic materials by stirring or shaking.
 7. The process as claimed in claim 6, wherein said macromolecular and inorganic materials include pigmenting coatings, paints, inks, including printing inks, and finish systems and wherein a liquid phase of said macromolecular and inorganic materials comprises water, organic solvent or mixtures of water and organic solvents.
 8. A process for pigmenting macromolecular organic and inorganic materials using color-mixing systems, comprising utilizing the solid pigment preparation as claimed in claim 1 as mixing components.
 9. A process for pigmenting plastics, comprising incorporating the solid pigment preparation as claimed in claim 1 into the plastics by extruding, rolling, kneading or milling.
 10. A process for pigmenting powder coatings, comprising incorporating the solid pigment preparation as claimed in claim 1 into the powder coatings by extruding, rolling, kneading or milling. 